DE1113820B - Process for the production of copolymers of vinylidene chloride - Google Patents

Description

It is known to use acrylic resins for the production of coatings and impregnations on fiber and to use film-shaped materials. They are of particular importance as binders in production obtained from dyeing and printing with pigments. In this field of application, as a rule high demands are placed on the fastness properties of the dyeings and prints; so should the colorations have good rub, wash and light fastness properties. It was found that in many cases the wash fastness after exposure of the dye is significantly reduced compared to the unexposed Coloring. In the following, this wash fastness of the exposed dyeing is referred to as light wash fastness designated.

It has now been found that with copolymers of the acrylic series, improved light wash fastnesses can be achieved if a monomer mixture is polymerized, which is composed of 28 to 50% vinylidene chloride, 0.2 to 10% of an acid of the formula

CH ₂ = C-COOH Method of manufacture

of copolymers

of vinylidene chloride

Applicant: CIBA Aktiengesellschaft, Basel (Switzerland)

Representative: Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse

and DipL-Chem. Dr. rer. nat. E. Frhr. v. Pechmann, patent attorneys, Munich 9, Schweigerstr. 2

Claimed priority: Switzerland of June 6, 1958

Dr. Arthur Maeder, Therwil,

and Dr. Georg Sulzer, Basel (Switzerland), have been named as the inventor

wherein R ₁ denotes hydrogen or a low molecular weight alkyl radical, and at least 35% of an ester of the formula

CH ₂ = CC-OR ₂

R ₁ O

where R _{1 has} the meaning given above and -OR ₂ denotes the remainder of an alcohol, and optionally from further monomers with only one olefinic double bond, the sum of the first three components being at least 80% of the monomer mixture.

In both of the formulas given above, R _{1 is} above all hydrogen or an alkyl radical having preferably 1 to 4 carbon atoms, such as the ethyl and, in particular, the methyl radical. -OR ₂ stands for the remainder of an alcohol of the formula HOR ₂ .

This alcohol can be aliphatic or cyclic. It can belong to the heterocyclic series. Examples include tetrahydrofurfuryl alcohol, cyclohexanol, alkoxy- or alkyl-substituted cyclohexanols, such as o-methylcyclohexanol, p-methoxycyclohexanol, furthermore decahydronaphthols, terpene alcohols such as isoborneol. - OR ₂ , however, preferably represents the radical of a saturated aliphatic alcohol having 1 to 18 carbon atoms, the alkyl group of which can be straight or branched and optionally interrupted by ether oxygen atoms. Methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl, tert. Butyl, amyl, 2-ethylbutyl, n-hexyl, heptyl, 2, ethylhexyl, dodecyl, octadecenyl or octadecyl alcohol, also methoxyethanol, ethoxyethanol, butoxyethanol, butoxybutanol. The esters of these alcohols HOR _{2 are} derived from α-alkyl acrylic acids, such as methacrylic acid, and preferably from acrylic acid. Of course, instead of one single ester of the specified composition, several of these can also be used with different alcohol and / or acid residues. For example, the cyclohexyl methacrylate can be combined with ethyl acrylate or the isobornyl acrylic ester with n-hexyl methacrylate. The esters of the formula have proven to be particularly advantageous

CH ₂ = CC-OR ₂

R ₁ O

wherein R _{1 is} hydrogen or a methyl group and R _{2 is} an alkyl radical having 3 to 7 carbon atoms, so z. B. the acrylic acid n-butyl ester or isobutyl ester.

109 688/232

As further components with only one olefinic double bond, optionally in an amount up to 20% of the monomer mixture can be used, including acrylonitrile, methacrylonitrile, Styrene, vinyl chloride, oil trifluoroethene, 1,1-difluoroethene, Acrylamide or methacrylamide and their nitrogen-substituted derivatives with 1 to 8 carbon atoms, such as N-diethylacrylamide, N-propylacrylamide, N-di-n-butyl acrylamide or N-tert-butyl acrylamide, furthermore vinyl alkyl ethers with about 2 to 10 carbon atoms in the alkyl group, such as vinyl ethyl, Vinyl butyl, vinyl 2-ethylbutyl or vinyl 2-ethylhexyl ether, or finally vinyl esters of aliphatic carboxylic acids with 2 to 4 carbon atoms, like vinyl acetate. Are components used that result in hard polymers such. B. Acrylonitrile, so the proportion of vinylidene chloride is expediently kept at the lower limit mentioned above.

The copolymers can be produced either in the block or by the suspension process take place. However, the polymerization in solution and especially in emulsion is preferred. Emulsion polymerization offers great advantages because it results from polymers obtained in this way Have easy-to-use coating and impregnating agents produced. The emulsion polymerization is useful with HMe from catalysts and carried out in the presence of emulsifiers.

As emulsifiers, with their HiMe the emulsions of the starting materials are prepared, those come into consideration which are sufficient in an acidic medium Have persistence, e.g. B. acidic fatty alcohol sulfuric acid esters, sulfonated castor oil, higher alkyl sulfonates, higher oxyalkyl sulfonates, in particular ce-oxyoctadecanesulfonic acid sodium, preferably that which is free from other salts; Sulfodicarboxylic acid esters, e.g. B. the sodium salt of Sulfosuccinic acid dioctyl esters, higher alkyl aryl sulfonates, also polyglycol ethers of higher molecular weight fatty alcohols, such as cetyl, oleyl or octadecyl alcohol, For example, products of the action of 15 to 30 moles of ethylene oxide per mole of the fatty alcohol. Emulsifiers with a pronounced wetting effect, such as octylphenol polyglycol ether, their acidic sulfuric acid esters, and also lauric alcohol polyglycol ethers, are used. It can also mixtures of such emulsifiers, also mixtures of such emulsifiers with protective colloids, such as esters of alginic acid, polyvinyl alcohols, partially saponified polyvinyl esters, proteins, Starch or starch derivatives, but it is preferred not to add such protective colloids, since their presence usually causes a significant deterioration in the film properties of the mixed polymers causes.

As polymerization catalysts, under their action the polymerization takes place, the usual polymerizations-catalyzing compounds, such as organic or inorganic peroxides or persalts, for example peracetic acid, Acetyl peroxide, benzoyl peroxide, benzoylacetyl peroxide, lauroyl peroxide, hydrogen peroxide, percarbonates, Persulfates or perborates can be added. Your addition is measured in a known manner the desired course of the reaction or the desired properties of the copolymer.

If necessary, several polymerization-catalyzing agents can be brought into action. The effect of the polymerization catalysts can be caused by the simultaneous action of heat and / or actinic rays. It is even possible to heat the polymerization only and / or to effect actinic rays without the addition of catalyzing compounds.

To produce the polymer emulsions to be prepared according to the invention, the customary technical apparatus are used. The production can take place in two stages. In a In the first stage, the emulsion of the starting materials can be produced in a second step is subjected to polymerization. Because the acids to be polymerized, e.g. B. acrylic acid or methacrylic acid, are soluble in water, it is possible to use these acids in the water containing the Contains emulsifier and possibly other additives to be dissolved prior to the preparation of the emulsion. Man but it can also be added to the finished emulsion of the other components.

To produce the emulsion of the components which are sparingly soluble in water, these can be used Make a mixture of the components and then emulsify this mixture. However, it is also possible to prepare an emulsion with one component alone and the other components in this Disperse emulsion. It is also possible to separate the various components Preparing emulsions and these emulsions in a suitable ratio before the polymerization Mix. Finally, the following working method should also be considered:

All but one of the components are emulsified in a single emulsion, from the last component a separate emulsion is prepared, which only in the course of the polymerization of the other Emulsion is added. This way of working can be advantageous when a component polymerizes faster and more easily than the other components. They are preferably used in the preparation of the emulsion the various components in a monomeric state for use. But you can also use one or the other connection in part Use pre-polymerized. The emulsions used for polymerization are everything those of the oil-in-water type.

The polymerization can be carried out at ordinary temperature; but it is more advantageous to polymerize at elevated temperature. For example, temperatures from 40 to 95 ° C are suitable, especially those from 55 to 90 ° C. The polymerizations often require considerable amounts of heat free, so that suitable cooling devices should be available in order to be able to maintain the desired polymerization temperatures. This is by name required when a larger amount of emulsion is polymerized at once. To the free take advantage of the amount of heat that will be generated and be able to regulate the polymerization temperature more easily, it has proven to be useful to use a certain amount of an emulsion to be processed to submit only a smaller part in the polymerization apparatus and the polymerization in to have this part used. When the temperature in this TeE the emulsion has a certain Height, for example 60 to 70 ° C, has reached, leaves

the rest of the cold emulsion is poured in in such a way that that the temperature can be kept constant. Towards the end of the polymerization there is often one external heat supply necessary.

As mentioned above, the polymerization depends on the type and amount of the polymerization catalyst, which is generally only added to the emulsion before the start of the polymerization, depending. About the reaction rate during the polymerization and the molecular weight of the copolymers To be able to modify, so-called regulators, z. B. mercaptans, are added.

It is also advantageous to carry out the polymerization in the absence of air and oxygen and in the presence of inert gases such as nitrogen or carbon dioxide. Furthermore, it is also possible to use so-called activators in addition to the above-mentioned catalysts and regulators. Such activators are, for example, inorganic, oxidizable, oxygen-containing sulfur compounds, such as SO ₂ , sodium bisulfate, sodium sulfate, ammonium bisulfite, sodium hydrosulfite or sodium thiosulfate. The simultaneous presence of the aforementioned activators and the oxygen-releasing polymerization catalysts result in so-called redox systems which have a favorable effect on the polymerization process. Water-soluble, aliphatic tertiary amines, such as triethanolamine or diethylethanolamine, can also be used as activators. It is also possible to increase the effect of the polymerization catalyst by using a heavy metal compound which can exist in more than one valency level and is present in a reduced state, or by adding complex cyanides of Fe, Co, Mo, Hg, Zn, Cu, Ag or from mixtures of such complexes.

The process according to the invention can be carried out continuously. The discontinuous However, the method of operation is preferred.

The dispersions of the copolymers prepared according to the invention react acidic and are in generally thin. Dispersions of suitable concentration can be achieved by full or partial Neutralization can be converted into ointment or paste-like masses, preferably concentrated aqueous ammonia solution is used.

The new emulsions of the copolymers are very strong, both in the acidic and in the alkaline setting stable and can therefore be used in a thin liquid as well as in an ointment or paste form will. These dispersions can also be mixed with numerous organic or inorganic pigments or mix fillers. If such pigments or fillers are to be used, one can make thickening after its addition, which facilitates the practical use of this emulsion and the possible uses are expanded. It is also possible to use other modifying substances, such as plasticizers, e.g. B. dibutyl or dioctyl phthalate, furthermore sebacic acid ester, to be added.

The products manufactured according to the invention are mainly suitable for the manufacture of well-adhering, elastic coatings on fabrics of all kinds, e.g. B. on cotton, jute, hemp, straw, polyester, Rayon, silk, rayon, polyamide, polyacrylonitrile or glass fabrics. In particular If desired, these dispersions can be thickened with ammonia and then using a knife coater be painted on such tissue or paper. This way you can use the new products z. B. waterproof raincoat fabrics, wax and oil cloth imitations, tent fabrics, oil silk fabrics and backing finishes on Manchester fabrics or carpets. As a result of their good Adhesion these resins are also suitable as primers under polyvinyl chloride coatings, z. B. for the production of artificial leather, and as a binder for leather covering paints on leather.

However, the new dispersions can also be used unthickened in the immersion process for the production of Filling finishes can be used on all types of fabrics. In this way z. B. ticking items, Fabrics with washable handle finishes, waterproof cellulose and interlinings that protect against dry washing are stable and do not become brittle. Other uses for the new Products consist of gluing polyvinyl chloride films or other synthetic resin films, as well as gluing of paper or metal foils with one another or with one another and also in the lamination of glass or All kinds of fabrics.

As already mentioned, the copolymers of the composition according to the invention are suitable in particular as a binder for pigment dyeings and prints on all types of textile materials, primarily Line fabrics made from native or regenerated cellulose, such as cotton, linen, rayon or rayon, also cellulose esters, such as acetate silk, wool, silk or synthetic fiber materials, such as polyamide, Polyester or polyacrylonitrile fibers, or glass fibers. The textile materials can just as well use these fibers mixed included.

From French patent specification 1138 278 it is known to produce copolymers which are made up of 60 to 94% vinylidene chloride, 5 to 35% acrylonitrile or alkyl acrylate and 1 to 25% acrylic acid or Compose methacrylic acid. They are used to make the photosensitive layer of a Photographic film to be firmly connected to the carrier layer and for this reason do not need to be film-forming and particularly elastic. But it is precisely these properties that are a prerequisite for the copolymers obtainable according to the invention.

In the examples below, parts mean parts by weight, unless otherwise noted Percentages by weight and temperatures are given in degrees Celsius.

example 1

A solution of 3.6 parts of a-oxyoctadecansulfonsaurem Sodium in 150 parts of water is mixed with 72 parts of isobutyl acrylate and 42 parts of vinylidene chloride and 6 parts of acrylic acid mixed. Another 0.4 part of triethanolamine and 0.2 part of isooctanol are added , mix the whole thing thoroughly and pour half of this emulsion into a mixing vessel 50 room parts content. This is with an ice-water cooled reflux condenser and a thermometer Mistake. The entire apparatus is thoroughly flushed with nitrogen before the emulsion is poured in.

The emulsion introduced is heated to an internal temperature of 60 ° and a solution of 0.06 parts of potassium persulfate in 6 parts of water are added. After about 15 minutes, a low temperature

rise, whereupon the remaining amount of the emulsion described above is added dropwise within 1 hour, which beforehand a solution of 0.06 parts of potassium persulfate in 6 parts of water is added. 15 minutes after the end of the dropping, the temperature has risen to about 66 °, and you are again a solution of 0.06 parts of potassium persulfate in 6 parts of water, whereupon the temperature rises again takes place until about 71 °. Two more times are then given at intervals of 2 hours each the same amount of catalyst is added (i.e. 0.06 parts of potassium persulfate in 6 parts of water), increased after the last addition the internal temperature by 10 ° and cools to room temperature after a further 2 hours.

A very finely dispersed, syrupy emulsion is obtained of about 40% resin content. The polymer yield is 93 to 95% of theory.

Pigment dyeings and prints made using the emulsion described above as a binder have good fastness to scrubbing, rubbing, washing and light washing.

Example 2

A solution of 3.6 parts of cs-oxyoctadecansulfonsaurem Sodium in 150 parts of water is mixed with 78 parts of isobutyl acrylate and 36 parts of vinylidene chloride and 6 parts of acrylic acid mixed. Another 0.4 part of triethanolamine and 0.2 part of isooctanol are added , mix the whole thing thoroughly and proceed according to Example 1 for the rest.

A very finely dispersed, syrupy emulsion with a resin content of about 40% is obtained. The polymer yield is about 93% of theory.

Example 3

A solution of 9 parts of a-oxyoctadecansulfonsaurem Sodium in 280 parts of water is mixed with 180 parts of isobutyl acrylate and 105 parts of vinylidene chloride and 15 parts of acrylic acid mixed. 1 part of triethanolamine and 0.6 part of isooctanol are also added , mix the whole thing thoroughly and pour half of this emulsion into a mixing vessel 1000 room parts content. This is with an ice-water cooled reflux condenser and a thermometer Mistake. The entire apparatus is thoroughly flushed with nitrogen before the emulsion is poured in.

The emulsion introduced is heated to an internal temperature of 60 ° and a solution of 0.12 parts of potassium persulfate in 2.4 parts of water are added. After about 15 minutes the temperature will be up about 5 °, whereupon the remaining amount of the emulsion described above is used for about 1 hour added dropwise, which previously added a solution of 0.12 parts of potassium persulfate in 2.4 parts of water will. 20 minutes after the end of the dropping, the temperature has risen by 6 °, and you are again a solution of 0.12 parts of potassium persulfate in 2.4 parts of water, whereupon the temperature rises again takes place up to about 75 °. Two more times are then given at intervals of 2 hours each the same amount of catalyst is added (i.e. 0.12 parts of potassium persulfate in 2.4 parts of water), increased after the last addition the internal temperature by 10 ° and cools to room temperature after a further 2 hours.

A very finely dispersed, low-viscosity emulsion with a resin content of about 50% is obtained. The polymer yield is about 98% of theory.

Example 4

A solution of 4.5 parts of a-oxyoctadecansulfonsaurem Sodium in 140 parts of water is mixed with 82.5 parts of isobutyl acrylate and 60 parts of vinylidene chloride and 6 parts of acrylic acid mixed. Another 0.5 part of triethanolamine and 0.3 part of isooctanol are added , mix the whole thing thoroughly and pour half of this emulsion into a mixing vessel 500 room parts content. This is with an ice-water cooled reflux condenser and a thermometer Mistake. The entire apparatus is thoroughly flushed with nitrogen before the emulsion is poured in.

The submitted emulsion is heated to 57 ° internal temperature and then a solution of Add 0.06 parts of potassium persulfate in 1.2 parts of water. After about 15 minutes there is a slight increase in temperature from 3 to 4 °, whereupon in 1 hour the remaining amount of the emulsion described above added dropwise, which previously a solution of 0.06 parts of potassium persulfate in 1.2 parts of water was added will. 20 minutes after the end of the dropping, the temperature has risen to about 68 °, and a solution of 0.06 part of potassium persulfate in 1.2 parts of water is again added, whereupon again a temperature increase of up to about 72 ° takes place. You give it up every 2 hours the same amount of catalyst was added twice (i.e. 0.06 parts potassium persulfate in 1.2 parts water) after the last addition, the internal temperature around 10 ° and cools to room temperature after a further 2 hours.

A very externally dispersed, thin syrupy emulsion with a resin content of about 50% is obtained. The polymer yield is 93 to 94% of theory.

Example 5

If the isobutyl acrylate in the emulsion described in Example 4 is replaced by the same amount n-butyl acrylate and otherwise proceeds exactly the same way, this also gives a finely dispersed, syrupy emulsion with a resin content of about 50%. The polymer yield is about 94% of theory.

- Example 6

If the isobutyl acrylate in the emulsion described in Example 4 is replaced by the same amount 2-ethylbutyl acrylate and if the rest of the procedure is exactly the same, one also obtains an externally dispersed, syrupy emulsion with about 50% resin content. The polymer yield is 92 to 93% of theory.

Example 7

If the monomer mixture in the emulsion described in Example 4 is replaced by such a mixture of 67.5 parts of 2-ethylbutyl acrylate, 75 parts of vinylidene chloride and 7.5 parts of acrylic acid and proceeds Otherwise exactly the same, a finely dispersed, syrupy emulsion with about 50% resin content is obtained.

Example 8

If the monomer mixture in the emulsion described in Example 4 is replaced by such a mixture of 7.5 parts of acrylic acid, 90 parts of n-butyl methacrylate and 52.5 parts of vinylidene chloride and proceeds otherwise exactly the same, one obtains a finely

disperse syrupy emulsion with about 50% resin content.

Example 9

If the monomer mixture in the emulsion described in Example 4 is replaced by such a mixture of 7.5 parts of methacrylic acid, 90.0 parts of n-butyl acrylate and 52.5 parts of vinylidene chloride and proceeds Otherwise exactly the same, the result is a finely dispersed, syrupy emulsion with a resin content of about 50%.

Example 10

If the monomer mixture in the emulsion described in Example 4 is replaced by such a mixture of 7.5 parts of acrylic acid, 15 parts of acrylonitrile, 75 parts of n-butyl acrylate and 52.5 parts of vinylidene chloride and if the rest of the procedure is exactly the same, a finely dispersed, syrupy emulsion of about 50% resin content.

Example 11

If the monomer mixture in the emulsion described in Example 4 is replaced by such a mixture of 7.5 parts of acrylic acid, 3 parts of acrylonitrile, 87 parts of n-butyl acrylate and 52.5 parts of vinylidene chloride and if the rest of the procedure is exactly the same, a finely dispersed, syrupy emulsion of about 50% resin content.

Example 12

If the monomer mixture in the emulsion described in Example 4 is replaced by such a mixture of 7.5 parts of acrylic acid, 7.5 parts of acrylonitrile, 82.5 parts of n-butyl acrylate and 52.5 parts of vinylidene chloride and if the rest of the procedure is exactly the same, a finely dispersed, syrupy emulsion of about 50% resin content.

Example 13

If the monomer mixture in the emulsion described in Example 4 is replaced by such a mixture from 7.5 parts of acrylic acid, 22.5 parts of acrylonitrile,

52.5 parts of vinylidene chloride and 67.5 parts of butyl acrylate and if the rest of the procedure is exactly the same, a finely dispersed, syrupy emulsion of about 50% resin content.

Example 14

If the monomer mixture in the emulsion described in Example 4 is replaced by such a mixture from 7.5 parts of acrylic acid, 30 parts of acrylonitrile,

52.6 parts of vinylidene chloride and 60 parts of n-butyl acrylate and if the rest of the procedure is exactly the same, a finely dispersed, syrupy emulsion of about 50% resin content.

Example 15

If the monomer mixture in the emulsion described in Example 4 is replaced by such a mixture of 7.5 parts of acrylic acid, 22.5 parts of di-n-butyl acrylamide, 67.5 parts of vinylidene chloride and 52.5 parts n-butyl acrylate and the rest of the procedure is exactly the same, the result is a finely dispersed, syrupy one Emulsion with about 50% resin content.

Example 16

If the monomer mixture in the emulsion described in Example 4 is replaced by such a mixture of 7.5 parts of acrylic acid, 22.5 parts of styrene, 45 parts of vinylidene chloride and 75 parts of n-butyl acrylate and if the rest of the procedure is exactly the same, a finely dispersed, syrupy emulsion of about 50% is obtained Resin content.

Claims (4)

PATENT CLAIMS: 1. Process for the preparation of copolymers from vinylidene chloride, an acid of general formula CH ₉ = C-COOH and an ester of the general formula
CH ₂ = CC-OR ₂ I Il R ₁ O wherein R ₁ denotes hydrogen or a low molecular weight alkyl group and -OR ₂ denotes the remainder of an alcohol, characterized in that a monomer mixture of 28 to 50% vinylidene chloride, 0.2 to 10% of an acid of the formula mentioned and at least 35% of an ester of mentioned formula and optionally from further monomers with only one olefinic double bond, the sum of the first three components being at least 80% of the monomer mixture, polymerized. 2. The method according to claim 1, characterized in that that one polymerizes in emulsion. 3. The method according to any one of claims 1 and 2, characterized in that one ester the formula f " ¹ / ~ * P R ₁ O where R _{1 is} hydrogen or a methyl group and R _{2 is} an alkyl radical having 3 to 7 carbon atoms, used as starting materials. 4. Process according to Claims 1 to 3, characterized in that there is a monomer component starts in a partially prepolymerized state. Considered publications:
French patent specification No. 1138 278. © 109 688/232 9.61